Compounds suitable as dispersion agent for pigments

ABSTRACT

The invention relates to compounds suitable as dispersion agent for pigments, of general formulae (I) to (III): R 1 —X—[—CO—NH—R 2 —NH—CO—Y—R 3 —Y—] r —CO—NH—R 2 —NH—CO—X—R 1  (I); R 1 —X—[—CO—NH—R 2 —NH—CO—Y—R 3 —Y—] r —CO—NH—R 4  (II); R 1 —X—[—CO—NH—R 2 —NH—CO—Y—R 3 —Y—] r —CO—NH—R 2 —NH—CO—Z—R 5  (III), where R 1 =an alkyl-capped oligoalkylenoxide residue of general formula (IV): R 6 O—(—CH 2 —CH 2 —O—) a —(R 7 —O—) b — (IV), and X, Y and Z each=O or NH, R 2 =arylene or arylalkylene group on a diisocyanate, R 3 =alkylene, arylene or arylalkylene group on a diol or diamine, R 4 =alkyl, aryl or arylalkyl group on a monoisocyanate, R 5 =alkyl, aryl or arylalkyl on a monoalcohol or monioamine, R 6 =alkyl with 1 to 4 C atoms, R 7 =branched alkylene group with 3 to 8 C atoms, r=a rational number from 0 to 100, a=a whole number from 1 to 300 and b=a whole number from 0 to 30.

This invention relates to compounds of the general formulae I to IIIR¹—X—[—CO—NH—R²—NH—CO—Y—R³—Y—]_(r)—CO—NH—R²—NH—CO—X—R¹  (I)R¹—X—[—CO—NH—R²—NH—CO—Y—R³—Y—]_(r)—CO—NH—R⁴  (II)R¹—X—[—CO—NH—R²—NH—CO—Y—R³—Y—]_(r)—CO—NH—R²—NH—CO—Z —R⁵  (III)

where R¹ is an alkyl-capped oligoalkylene oxide radical of the generalformula IVR⁶O—(—CH₂—CH₂—O—)_(a)—(—R⁷—O—)_(b)—  (IV)

where

X is O or NH

Y is O or NH

Z is O or NH

R² is an arylene or aralkylene radical of an aliphatic, aromatic oraromatic-aliphatic diisocyanate OCN—R²—NCO,

R³ is an alkylene, arylene or aralkyl radical of an aliphatic, aromaticor aromatic-aliphatic diol HO—R³—OH for Y being O or a diamineH₂N—R³—NH₂ for Y being NH,

R⁴ is an alkyl, aryl or aralkyl radical of an aliphatic, aromatic oraromatic-aliphatic monoisocyanate R⁴—NCO,

R⁵ is an alkyl, aryl or aralkyl radical of an aliphatic, aromatic oraromatic-aliphatic monoalcohol R⁵—OH for Z being O or a monoamine R⁵—NH₂for Z being NH,

R⁶ is alkyl of 1 to 4 carbon atoms,

R⁷ is branched alkylene of 3 to 8 carbon atoms,

r is a rational number from zero to 100,

a is an integer from 1 to 300, and

b is an integer from zero to 30.

The compounds having the general formula I are hereinafter referred toas compounds I for short, the compounds having the general formula IIare hereinafter referred to as compounds II for short, and the compoundshaving the general formula III are hereinafter referred to as compoundsIII for short.

The present invention further provides a process for preparing thecompound I, a process for preparing the compounds II and a process forpreparing the compounds III, the use of these compounds I, II and III asdispersants for pigments and also as process chemicals in pigmentmanufacture, and also pigment preparations including these compounds I,II or III. The present invention also provides for the use of thesepigment preparations for water-containing coatings and paints, inparticular waterborne coatings. The present invention finally provideswater-containing coatings, water-containing printing inks,water-containing paints and waterborne coatings that include thesepigment preparations.

Pigment preparations include dispersant additives to improve therheological and color properties of the pigments. In aqueous paints inparticular, dispersant additives are intended to facilitate thedispersion of the pigments and inhibit coagulation, flocculation orsedimentation of the pigments during the storage of the ready-producedpaint.

U.S. Pat. No. 4,929,279 describes a process for dispersing an organicpigment in an aqueous phase by using salts of certain propane-diaminesor polyethylene oxides as a dispersant-surfactant.

EP-A 154 678 discloses pigment dispersants prepared by reactingpolyisocyanates first with monohydroxy compounds, then with, inter alia,polyols such as polyalkylene glycols for example and finally withheterocyclic compounds. Monoterminally alkyl-capped polyols (HO—R—OR′)are not mentioned.

DE-A 2 906 111 teaches pigment preparations including urea derivativesof the formula K—(—NH—CO—NH—R)₂ where K is 1,5-naphthylene or4,4′-diphenylmethane and R may be —(CH₂)₃—O—(C₂H₄O)_(n)—O—R¹ (where n is1, 2, 3 or 4, R¹ is C₂-C₈-alkyl or phenyl). In contrast to the compoundsof the present invention, which have a branched alkylene radical R⁷, thepropylene radical —(CH₂)₃— is linear in this reference.

EP-A 555 950 describes aqueous pigment dispersions where the dispersantingredient is a polycyclic aromatic compound having a polyalkylene oxideside chain, for example ethoxylated 1- or 2-naphthol.

WO-A 99/41320 discloses ink jet inks containing polyurethane dispersantshaving, for example, polyalkylene oxide (for instance, polyethyleneglycol methyl ether) as a dispersing group. However, the polyurethanescontain ionic groups, especially carboxyl groups.

DE application 10147404.0, unpublished at the priority date of thepresent invention, describes polyurethane block copolymers for preparingdispersing binders that may contain hydrophilic end groups. However, theend groups contain an —OH group in the terminal position and not, likethe compounds of the present invention, —O(alkyl). For this reason, thepolyurethane block copolymers are partially crosslinkable.

The prior art compounds do not improve the color and Theologicalproperties of the pigment preparations to a sufficient degree for allapplications. More particularly, the dispersibility of the pigments isnot always sufficiently improved by the prior art dispersants.

In addition, the known compounds have comparatively low melting orsoftening points and are liquid or pasty, which is why the pigmentformulations prepared therewith become doughy and gooey. Doughy or gooeypigment formulations are not uniformly incorporable in the coating to bepigmented.

Moreover, in the known liquid dispersant media, some pigments aresusceptible to undesirable recrystallization coupled withdisadvantageous particle growth.

Furthermore, the known dispersants only permit the production ofrelatively low-pigment formulations, ie pigment formulations having ahigh pigment volume concentration cannot be produced. Finally, the knowncompounds can be used in pigment manufacture only with limited success,if any. More particularly, the known liquid dispersants cannot be usedin some important operations of pigment manufacture such as dry ballmilling.

It is an object of the present invention to remedy the disadvantagesdescribed. More particularly, it is an object of the present inventionto provide compounds which, when used as pigment dispersants, improvethe color properties (color strength, chroma, transparency, etc) and theTheological properties (including yield point, viscosity) of the pigmentpreparations.

It is a further object of the present invention to provide compoundswhich improve the dispersibility of the pigments.

The compounds shall moreover not cause the pigment preparations tobecome gooey or doughy, even when included in the preparation in arelatively high concentration. Pigment recrystallization shall becontrolled.

Moreover, the compounds shall make it possible to prepare high-pigmentpreparations as well.

The compounds shall lastly also be useful in pigment manufacture, forexample as assistants at the synthesis or crystallization stage, asassistants in the wet treatment (eg wet grinding, kneading, suspension)or dry grinding, and also as assistants at the drying stage (eg toreduce agglomeration during drying and during dry grinding).

We have found that these objects are achieved by the compounds definedat the beginning.

The present invention further provides a process for preparing thecompound I, a process for preparing the compounds II and a process forpreparing the compounds III, the use of these compounds I, II and III asdispersants for pigments and also as process chemicals in pigmentmanufacture, and also pigment preparations including these compounds I,II or III. The present invention also provides for the use of thesepigment preparations for coloring water-containing coatings, printinginks and paints, in particular waterborne coatings, and alsowater-containing coatings, water-containing paints and waterbornecoatings that include these pigment preparations.

Preferred embodiments of the invention are discernible from subsidiaryclaims.

In contrast to the aforementioned WO-A 99/41320 reference, the compoundsof the present invention do not contain ionic groups such ascarboxylate, phosphate, phosphonate, sulfonate or quaternary ammonium(see WO-A 99/41320 page 9 line 29-page 10 line 4 and page 15 line14-page 17 line 9).

The compounds of the general formula IR¹—X—[—CO—NH—R²—NH—CO—Y—R³—Y—]_(r)—CO—NH—R²—NH—CO—X—R¹  (I)have an ABA block structure in which the alkyl-capped oligoalkyleneoxide radicals R¹ constitute the A blocks and the internal structure—X—[—CONH—R²—NHCO—Y—R³—Y—]_(r)—CONH—R²—NHCO—X—constitutes the B block:

When X is O or Y is O, there is a urethane group (carbamate group) V,

and when X is NH or Y is NH, there is a urea group VI

The meaning of the variables X and Y in the above formula I (O or NH)follows from the starting materials, see hereinbelow.

Preferably either each X is O or each X is NH (and not, for instance,one X being O and one X being NH). The same holds for Y, mutatismutandis. However, each X and each Y can both be O or NH, or each X canboth be O and each Y can both be NH, or each X can both be NH and each Ycan both be O.

The starting materials from which the compounds I are prepared will nowbe described.

R² is the arylene or aralkylene radical of respectively an aliphatic,aromatic or aromatic-aliphatic diisocyanate OCN—R²—NCO. Usefuldiisocyanates OCN—R²—NCO include in particular:

hexamethylene diisocyanate (HDI), R²: —(—CH₂—)₆—

naphthylene 1,5-diisocyanate (NDI); R²:

tolylene 2,4-diisocyanate (TDI); R²:

tolylene 2,6-diisocyanate (TDI); R²:

methylene diphenyl diisocyanate (MDI);

tetramethyl-m-xylene diisocyanate (TMXDI):

p-phenylene diisocyanate (PPDI): R²:

isophorone diisocyanate (IPDI),

As well as p-phenylene diisocanate, it is also possible to use thecorresponding o- and m-isomers. In the case of MDI, not only monomericMDI but also polymeric MDI (PMDI) is suitable.

The aforementioned diisocyanates HDI, NDI, TDI, MDI or PMDI, TMXDI, PPDIand IPDI are particularly preferred. Accordingly, the aforementioned R²radicals are particularly preferred.

R³ is the alkylene, arylene or aralkylene radical of an aliphatic,aromatic or aromatic-aliphatic diol HO—R³—OH in the case of Y being O orof an aliphatic, aromatic or aromatic-aliphatic diamine H₂N—R³—NH₂ inthe case of Y being NH.

Useful diols HO—R³—OH (Y being O) are preferably aliphatic diols,especially

Ethylene glycol, 1,4-butanediol and 1,6-hexanediol, R³: —CH₂—(CH₂)_(n)—where n=1, 2, 3, 4 or 5 (but n can also be from 6 to 10),

-   -   neopentylglycol R³:

Useful diols further include for example 1,3-propanediol,1,5-pentanediol, 1,7-heptanediol, 1,2-cyclohexanediol,1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-propanediol,1,2-butanediol, 1,2-pentanediol, 1,2 hexanediol, 1,2-heptanediol,1,2-dodecanediol, 1,2-octadecanediol, 1,8-octanediol,2,7-dimethyl-3,5-octadiyne-2,7-diol, 2-butyl-2-ethyl-1,3-propanediol and2-ethylhexanediol.

In contrast to WO-A 99/41320 (page 15 line 14-page 17 line 9), however,ionic diols such as dimethylolpropionic acid are unsuitable.

Useful diamines H₂N—R³—NH₂ (Y being NH) are preferably aromatic and morepreferably aliphatic diamines. Useful aromatic diamines are inparticular phenylenediamines.

Useful aliphatic diamines are in particular ethylenediamine and1,6-hexamethylenediamine (R³: —CH₂—(CH₂)_(n)— where n=1 or 5).

Useful diamines further include for example 1,5-diaminonapthalene,tolylene-2,4-diamine, tolylene-2,6-diamine, methylenediphenyldiamine,tetramethyl-m-xylenediamine, o-phenylenediamine, m-phenylenediamine,p-phenylenediamine, 1,3-propanediamine, 1,4-butanediamine,1,5-pentanediamine, 1,8-octanediamine, 4,7-dioxadecane-1,10-diamine,4,11-dioxatetradecane-1,14-diamine, polyoxyethylenediamine,polyoxypropylenediamine, bis(3-aminopropyl)polytetrahydrofuran,polytetrahydrofurandiamine, N,N-dimethyldipropylenetriamine,ethylaminoethylamine, N,N-dimethylethylenediamine,2-dimethylaminoethylamine, 2-diisopropylaminoethylamine,N,N-di-tert-butylethylenediamine, N,N-dimethylpropane-1,3-diamine and3-isopropylaminopropylamine.

It is also possible to use mixtures of diols and diamines oraminoalcohols HO—R³—NH₂ to thereby form compounds I where one Y is O andone Y is NH. However, this is less preferable.

R¹ is an alkyl-capped, ie alkyl-terminated, oligoalkylene oxide radicalof the general formula IVR⁶O—(—CH₂—CH₂—O—)_(a)—(—R⁷—O—)_(b)—  (IV)

In the formula, R⁶ is an alkyl radical of 1 to 4 carbon atoms,especially methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl orsec-butyl.

R⁶ is most preferably methyl, ie the oligoalkylene oxide radical ismethyl-capped.

The ethylene oxide group —(—CH₂—CH₂—O—)_(a)— is mandatorily present inthe oligoalkylene oxide radical R¹, ie a is at least 1. a is customarilyfrom 1 to 300, preferably from 1 to 200 and more preferably from 5 to50.

R⁷ is a branched, ie nonlinear, alkyl radical of 3 to 8 carbon atomssuch as for example propylene. The alkylene oxide group —(—R⁷—O—)_(b)—is optional, ie b can also be zero. That is preferred. Otherwise, b iscustomarily up to 15, preferably up to 3 and more preferably up to 1.

Particularly preferably, a is from 1 to 300 and b zero.

The alkylene oxide group —(—R⁷—O—)_(b)— can also be constructed of aplurality of alkylene oxides R⁷′, R⁷″, R⁷′″, etc, ie have the structure—(R⁷′—O)_(b1)—(R⁷″—O)_(b2)—(R⁷′″—O)_(b3)—

where b1, b2 and b3 are each customarily in the range from 1 to 10 andpreferably from 1 to 3.

The oligoalkylene oxide radicals of the above formula IV are derivedfrom the corresponding oligoalkylene oxides IVa and Ivb respectively:R⁶O—(—CH₂—CH₂—O—)_(a)—(—R⁷—O—)_(b)—OH  (IVa)

when X is O

orR⁶O—(—CH₂—CH₂—O—)_(a)—(—R⁷—O—)_(b)—NH₂  (IVb)

when X is NH.

Alkyl-capped oligoalkylene oxides having an —OH end group (above formulaIVa) can be prepared in a conventional manner, for example by graftingonto an alcohol R⁶OH (eg methanol for methyl-capped oligoalkyleneoxides), ethylene oxide and, when b is more than zero, higher alkyleneoxides as well.

Alkyl-capped oligoalkylene oxides are also commercially available, forexample as Pluriol® AnE from BASF, in which case n is generally in therange from 100 to 5000 and especially in the range from 250 to 2500.Illustrative examples are the Pluriol® grades A2000E, A1000E, A750E,A500E, A350E and A275E.

Alkyl-capped oligoalkylene oxides of the above formula IVa where b isgreater than zero can for example be prepared by first convertingmonoalkyldiethylene glycol R⁶O—CH₂—CH₂—OH to oligoalkylene oxides of theformula R⁶O—(—CH₂—CH₂—O—)_(a)—OH in the presence of bases such as NaOHand then reacting these oligoalkylene oxides with alkylene oxides R⁷Osuch as propylene oxide (R⁷=propylene) to form the oligoalkylene oxideIVa R⁶O—(—CH₂—CH₂—O—)_(a)—(—R⁷—O—)_(b)—OH.

The above alkyl-capped oligoalkylene oxides featuring OH termination canbe subjected to catalytic reductive amination to prepare alkyl-cappedoligoalkylene oxides IVb featuring NH₂ terminationR⁶O—(CH₂—CH₂—O)_(a)—(R⁷—O)_(b)—NH₂  (IVb)

More particularly, such aminated alkyl-capped oligoalkylene oxides canfor example be prepared by direct reaction of the corresponding alcohol(—OH end group) with ammonia. This amination is customarily carried outover a heterogeneous catalyst, especially over catalysts containingoxygen-containing compounds of zirconium, of copper, of cobalt and ofnickel (ZrO₂/CuO/CoO/NiO catalyst). The reaction is for exampledescribed in EP-A 382 049, expressly incorporated herein by reference.

The starting materials mentioned are used in a preferred embodiment toprepare the compounds I by reacting a diisocyanate OCN—R²—NCO with adiol HO—R³—OH, when Y is O or with a diamine H₂N—R³—NH₂, when Y is NHand with an alkyl-capped oligoalkylene oxide of the general formula IVawhen X is O,R⁶O—(—CH₂—CH₂—O—)_(a)—(—R⁷—O—)_(b)—OH  (IVa)

or of the general formula IVb when X is NH,R⁶O—(—CH₂—CH₂—O—)_(a)—(—R⁷—O—)_(b)—NH₂  (IVb).

The proportions in which the starting materials are used depend as usualon the desired reaction product (compound I) and are generally based onthe molar amount of the diisocyanate used, as is customary in theisocyanate art. For example, r mol of diol or diamine can be used per(r+1) mol of diisocyanate, and so on.

The diisocyanate can be reacted first with the diol or diamine and thenwith the oligoalkylene oxide. Similarly, the diisocyanate can be firstreacted with the oligoalkylene oxide and then with the diol or diamine.However, both the diol/diamine and the oligoalkylene oxide can be addedto the diisocyanate and simultaneously reacted with the diisocyanate.The order is accordingly freely choosable.

The reaction of the diisocyanates with the diols or diamines is carriedout in a conventional manner, for example by using catalysts. Usefulcatalysts include for example tertiary amines, eg triethylamine,dimethylcyclohexylamine, N-methylmorpholine, N,N-dimethylpiperazine,2-(dimethylaminoethoxy)ethanol, diazabicyclo(2,2,2)octane and the like,and also in particular organic metal compounds such as titanate esters,iron compounds, eg iron(III) acetylacetonates, tin compounds, eg tindiacetate, tin dioctoate, tin dilaurate or the dialkyl derivatives oftin dialkyl salts of aliphatic carboxylic acids such as dibutyltindiacetate, dibutyltin dilaurate or the like. The catalysts arecustomarily used in amounts from 0.0001 to 0.1 part by weight per 100parts by weight of diol or diamine.

The reaction is customarily carried out in an aprotic solvent, forexample in tetrahydrofuran, diethyl ether, diisopropyl ether,chloroform, dichlormethane, di-n-butyl ether, acetone,N-methylpyrrolidone (NMP), xylene, toluene, methyl ethyl ketone (MEK),methyl isobutyl ketone (MIBK), N,N-dimethylformamide (DMF) or1,4-dioxane. However, protic solvents such as water or alcohols aresuitable as well.

Preferred reaction temperatures range from −80° C. to the boiling pointof the solvent used. The reaction is generally carried out underatmospheric pressure, but reactions in autoclaves at up to 20 bar aresuitable as well.

The number r can range from 0 to 100. When r is greater than zero,oligomeric or polymeric compounds I having an ABA block structure areobtained. The number r of repeat units is not more than 100 andcustomarily up to 20.

When r is zero—and these compounds I are preferred—the low molecularweight or monomeric compounds I obtained have pronounced surface-activeproperties and will hereinafter be referred to as surfactants for short.The surfactants are preferably prepared in accordance with the abovedirections, although no diol HO—R³—OH or diamine H₂N—R³—NH₂ is used onaccount of r being zero. That is, the diisocyanate OCN—R²—NCO is reactedwith the alkyl-capped oligoalkylene oxide IVa or IVb to form thesurfactant I (where r is 0).

r is preferably 0, ie the surfactant compounds I preferably have theformula IaR¹—X—CO—NH—R²—NH—CO—X—R¹  (Ia)

When R² is 1,5-naphthylene (derived from naphthylene 1,5-diisocyanate),the product formed is thus a surfactant of the formula Ib:

Particular preference is given to compounds I where R⁶ is methyl and ris 0, ie to ABA surfactants having methyl-capped oligoalkylene oxideradicals R¹.

The compounds of the general formula IIR¹—X—[—CO—NH—R²—NH—CO—Y—R³—Y—]_(r)—CO—NH—R⁴  (II)

have an AB block structure in which the alkyl-capped oligoalkylene oxideradical R¹ constitutes the A block and the structure—X—[—CONH—R²—NHCO—Y—R³—Y—]_(r)—CONH—R⁴ constitutes the B block:R¹—X—[CONH—R²—NHCO—Y—R³—Y—]_(r)—CONH—R⁴A|B

The explanations given above in relation to the compounds I with regardto the variables X, Y, R¹, R², R³, R⁶, R⁷, r, a and b, with regard tothe starting materials and with regard to the method of making applymutatis mutandis to the compounds II as well, except when otherwisespecified.

Compound II differs from compound I in having an —R⁴ group in theformula II instead of the —R²—NH—CO—X—R¹ group in the formula I.

R⁴ is the alkyl, aryl or aralkyl radical of an aliphatic, aromatic oraromatic-aliphatic monoisocyanate R⁴—NCO.

Useful monoisocyanates R⁴—NCO include for example: methyl isocyanate,ethyl isocyanate, propyl isocyanate, n-butyl isocyanate, tert-butylisocyanate, isobutyl isocyanate, pentyl isocyanate, neopentylisocyanate, 2-ethylhexyl isocyanate, phenyl isocyanate, tolylisocyanate, 1-napthyl isocyanate and 2-napthyl isocyanate and alsothioisocyanates such as methyl thioisocyanate, ethyl thioisocyanate,propyl thioisocyanate, n-butyl thioisocyanate, tert-butylthioisocyanate, isobutyl thioisocyanate, pentyl thioisocyanate,neopentyl thioisocyanate, 2-ethylhexyl thioisocyanate, phenylthioisocyanate, tolyl thioisocyanate, 1-napthyl thioisocyanate and2-napthyl thioisocyanate.

1-Naphthyl isocyanate and 2-naphthyl isocyanate are particularlypreferred.

The starting materials mentioned are used in a preferred embodiment toprepare the compounds II by reacting a diisocyanate OCN—R²—NCO with adiol HO—R³—OH, when Y is O or with a diamine H₂N—R³—NH₂, when Y is NHand with an alkyl-capped oligoalkylene oxide of the general formula IVawhen X is O,R⁶O—(—CH₂—CH₂—O—)_(a)—(—R⁷—O—)_(b)—OH  (IVa)

or of the general formula IVb when X is NH,R⁶O—(—CH₂—CH₂—O—)_(a)—(—R⁷—O—)_(b)—NH₂  (IVb)

and also with a monoisocyanate R⁴—NCO.

The aforementioned process for preparing the compounds II consequentlydiffers from the above-described process for preparing the compounds Iby additionally including a reaction with a monofunctional compoundR⁴—NCO.

The proportions of the materials used as starting materials depend asusual on the desired reaction product (compound II) and are generallybased on the molar amount of the diisocyanate used, as is customary inthe isocyanate art. For example, r mol of diol or diamine can be usedper r mol of diisocyanate, etc.

The order of the reactions to prepare the compound II is freelychoosable. For instance, the diisocyanate can be reacted first with thediol or diamine and then with the oligoalkylene oxide and themonoisocyanate. It is similarly possible to react the diisocyanate firstwith the diol or diamine and with the monoisocyanate before adding theoligoalkylene oxide. It is likewise possible to add the oligoalkyleneoxide and the diol or diamine to a mixture of diisocyanate andmonoisocyanate.

The integer r can be from 0 to 100. When r is greater than zero,oligomeric or polymeric compounds II having an AB block structure areobtained. r is not more than 100 and customarily up to 20.

When r is zero—and these compounds II are preferred—the low molecularweight or monomeric compounds II obtained have surface-active properties(surfactants). The surfactants are preferably prepared as describedabove, although no diol HO—R³—OH or diamine H₂N—R³—NH₂ nor anydiisocyanate OCN—R²—NCO is used on account of r being 0. That is, thealkyl-capped oligoalkylene oxide IVa or IVb is reacted with themonoisocyanate R⁴—NCO to form the surfactant II (where r is 0).

r is preferably 0, ie the surfactant compounds II preferably have theformula IIaR¹—X—CO—NH—R⁴  (IIa)

When R⁴ is naphthyl (derived from naphthyl isocyanate), the productobtained is thus a surfactant of the formula IIb:

Particular preference is given to compounds II where R⁶ is methyl and ris 0, ie to AB surfactants having methyl-capped oligoalkylene oxideradicals R¹.

The compounds of the general formula IIIR¹—X—[—CO—NH—R²—NH—CO—Y—R³—Y—]_(r)—CO—NH—R²—NH—CO—Z—R⁵  (III)have an AB block structure in which the alkyl-capped oligoalkylene oxideradical R¹ constitutes the A block and the structure—X—[—CONH—R²—NHCO—Y—R³—Y—]_(r)—CONH—R²—NHCO—Z—R⁵ constitutes the Bblock:R¹—X—[CONH—R²—NHCO—Y—R³—Y—]_(r)—CONH—R²—NHCO—Z—R⁵A|B

The explanations given above in relation to the compounds I with regardto the variables X, Y, R¹, R², R³, R⁶, R⁷, r, a and b, with regard tothe starting materials and with regard to the method of making applymutatis mutandis to the compounds III as well, except when otherwisespecified.

Z can be O or NH.

Compound III differs from the compounds I and II by having an—R²—NH—CO—Z—R⁵ group in the formula III instead of respectively the—R²—NH—CO—X—R¹ group in the formula I and the R⁴ group in the formulaII.

R⁵ is the alkyl, aryl or aralkyl radical of an aliphatic, aromatic oraromatic-aliphatic monoalcohol R⁵—OH when Z is O or respectively analiphatic, aromatic or aromatic-aliphatic monoamine R⁵—NH₂ when Z is NH.

Useful monoalcohols R⁵—OH include for example: methanol, ethanol,n-propanol, i-propanol, n-butanol, sec-butanol, tert-butanol, pentanol,hexanol, heptanol, dodecanol, octadecanol, benzyl alcohol, lesspreference being given to phenols: phenol, α-napthol, β-napthol,cyclohexanol, tert-amyl alcohol, propargyl alcohol, butyn-3-ol,3-Methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-2-ol,2-methyl-3-butyn-2-ol, ethynyl-1-cyclohexanol, ethyloctynol,1-methoxy-2-propanol, 4-methylbenzyl alcohol, 4-tert-butylbenzylalcohol, 2-(4-methoxyphenyl)ethanol, neopentyl alcohol,1-butoxy-2-propanol, 1-methoxy-2-butanol, 3-methyl-3-pentanol,6-chloro-1-hexanol, 8-chloro-1-octanol, 2-methylcyclohexanol and3-methyl-1-pentyn-3-ol.

Useful monoamines R⁵—NH₂ include for example:

-   -   primary aliphatic amines such as methylamine, ethylamine,        n-propylamine, isopropylamine, n-butylamine, isobutylamine,        sec-butylamine, amylamine, n-pentylamine, isopentylamine,        neopentylamine, 3-methyl-2-butylamine, hexylamine, octylamine,        dodecylamine, tridecylamine, octadecylamine,        mono-2-ethylhexyl-amine, 6-methyl-2-heptanamine,        cyclopropylamine and cyclopentylamine;    -   secondary aliphatic amines such as dimethylamine, diethylamine,        di-n-propylamine, diisopropylamine, dibutylamine,        diisobutyl-amine, di-sec-butylamine, dipentylamine,        diisopentylamine, dihexylamine, di-2-ethylhexylamine,        ditridecylamine, N-ethyl-isopropylamine,        1-methoxy-2-aminopropane, N-ethyl-1,2-dimethyl-propylamine,        n-methylbenzylamine, tert-butylbenzylamine,        4-methoxybenzylamine, phenylethylamine,        1-methyl-3-phenyl-propylamine, N-methylaniline, 2,6-xylidine and        3,5-xylidine;    -   primary aromatic amines such as aniline, 1-chloroaniline,        2-chloroaniline, 3-chloroaniline, 2,3-dichloroaniline,        3,4-dichloroaniline, 3,5-dichloroaniline, 2,5-dichloroaniline,        2,6-dichloroaniline, the corresponding bromoanilines,        1-naphthylamine, 2-naphthylamine, substituted naphthylamines,        2,6-diisopropylaniline, benzylamine, o,m,p-toluidine and the        class of the alkoxyanilines (especially methoxyanilines) and of        the nitroanilines;    -   finally ammonia, N-ethylbutylamine, β-hydroxyethylamine, β- or        γ-hydroxypropylamine, N-methylethanolamine, diethanolamine,        3-(2-hydroxyethylamino)-1-propanol, ethanolamine,        diethanolamine, N-(2-hydroxyethyl)aniline, hydroxylamine,        hydrazine, 3-ethoxypropylamine, di-(2-methoxyethyl)amine,        cyclohexylamine, N-ethylcyclohexylamine, dicyclohexylamine,        2-phenylethylamine, 4-methoxyphenylethylamine,        1-phenyl-3-phenylpropylamine, 2-(3,4-dimethoxyphenyl)ethylamine,        N-ethylaniline, 2-(2-aminoethoxy)ethanol and        2-(2-(3-aminopropoxy)ethoxy)ethanol.

The starting materials mentioned are used in a preferred embodiment toprepare the compounds III by reacting a diisocyanate OCN—R²—NCO with adiol HO—R³—OH when Y is O or with a diamine H₂N—R³—NH₂ when Y is NH andwith an alkyl-capped oligoalkylene oxide of the general formula IVa whenX is O,R⁶O—(CH₂—CH₂—O)_(a)—(R⁷—O)_(b)—OH  (IVa)

or of the general formula IVb when X is NH,R⁶O—(CH₂—CH₂—O)_(a)—(R⁷—O)_(b)—NH₂  (IVb)

and also, when Z is O, with the monoalcohol R⁵—OH or, when Z is NH, withthe monoamine R⁵—NH₂.

The abovementioned process for preparing the compounds III consequentlydiffers from the above-described process for preparing the compounds Iin that it additionally comprises a reaction with a monofunctionalcompound R⁵—OH or R⁵—NH₂. It differs from the process for preparing thecompounds II in that the monofunctional compound it utilizes is R⁵—OH orR⁵—NH₂ (instead of R⁴—NCO).

The proportions in which the materials used as starting materials areused depend as usual on the desired reaction product (compound III) andare generally based on the molar amount of diisocyanate used, as iscustomary in the isocyanate art. For example, r mol of diol or diaminecan be used per (r+1) mol of diisocyanate, etc.

The order of the reactions to prepare the compound III is freelychoosable. For instance, the diisocyanate can be reacted first with thediol or diamine and then with the oligoalkylene oxide and the monoamineor monoalcohol. It is similarly possible first to react the diisocyanatewith the diol or diamine and the monoamine or monoalcohol before addingthe oligoalkylene oxide. It is likewise possible to add theoligoalkylene oxide to a mixture of diol and monoalcohol or diamine andmonoamine.

The integer r can be from 0 to 100. When r is greater than zero,oligomeric or polymeric compounds III having an AB block structure areobtained. r is not more than 100 and customarily up to 20.

When r is zero—and these compounds III are preferred—the low molecularweight or monomeric ompounds III obtained have surface-active properties(surfactants). The surfactants are preferably prepared as describedabove, although no diol HO—R³—OH or diamine H₂N—R³—NH₂ nor adiisocyanate OCN—R²—NCO is used on account of r being 0. That is, thealkyl-capped oligoalkylene oxide IVa or IVb is reacted with themonoalcohol R⁵—OH or monoamine R⁵—NH₂ to form the surfactant III (wherer is 0).

r is preferably 0, ie the surfactant compounds III preferably have theformula IIIaR¹—X—CO—NH—R²—NH—CO—Z—R⁵  (IIIa)

Particular preference is given to compounds III where R⁶ is methyl and ris 0, ie to AB surfactants having methyl-capped oligoalkylene oxideradicals R¹.

r in the compounds I, II and III is a positive rational number since theprocess of making the compounds may give rise to distributions which arenot described by integral r.

According to the invention, the compounds I, II and III can be used asdispersants for pigments.

The present invention likewise provides for the use of the compounds I,II and III as process chemicals (assistants, auxiliaries) in pigmentmanufacture.

Pigments are defined in the German standards DIN 55943 (September 1984),DIN 55944 and DIN 55945 (August 1983) as inorganic or organic, chromaticor achromatic colorants which are virtually insoluble in the applicationmedium. Pigments will hereinbelow be named in accordance with ColourIndex (C.I.) nomenclature, although the “C.I.” constituent may beomitted in some instances.

There now follow examples of useful pigments, vat dyes being, for thepurposes of this invention, considered as organic pigments. Organicpigments: monoazo pigments: C.I. Pigment Brown 25; C.I. Pigment Orange5, 13, 36 and 67; C.I. Pigment Red 1, 2, 3, 5, 8, 9, 12, 17, 22, 23, 31,48:1, 48:2, 48:3, 48:4, 49, 49:1, 52:1, 52:2, 53, 53:1, 53:3, 57:1, 63,112, 146, 170, 184, 190, 210, 245 and 251; C.I. Pigment Yellow 1, 3, 73,74, 65, 97, 151 and 183; disazo pigments: C.I. Pigment Orange 16, 34 and44; C.I. Pigment Red 144, 166, 214 and 242; C.I. Pigment Yellow 12, 13,14, 16, 17, 81, 83, 106, 113, 126, 127, 155, 174, 176 and 188;anthanthrone pigments: C.I. Pigment Red 168 (C.I. Vat Orange 3);anthraquinone pigments: C.I. Pigment Yellow 147 and 177; C.I. PigmentViolet 31; anthrapyrimidine pigments: C.I. Pigment Yellow 108 (C.I. VatYellow 20); quinacridone pigments: C.I. Pigment Red 122, 202 and 206;C.I. Pigment Violet 19; quinophthalone pigments: C.I. Pigment Yellow138; dioxazine pigments: C.I. Pigment Violet 23 and 37; flavanthronepigments: C.I. Pigment Yellow 24 (C.I. Vat Yellow 1); indanthronepigments: C.I. Pigment Blue 60 (C.I. Vat Blue 4) and 64 (C.I. Vat Blue6); isoindoline pigments: C.I. Pigment Orange 69; C.I. Pigment Red 260;C.I. Pigment Yellow 139 and 185; isoindolinone pigments: C.I. PigmentOrange 61; C.I. Pigment Red 257 and 260; C.I. Pigment Yellow 109, 110,173 and 185; isoviolanthrone pigments: C.I. Pigment Violet 31 (C.I. VatViolet 1); metal complex pigments: C.I. Pigment Yellow 117, 150, 153 and177; C.I. Pigment Green 8; perinone pigments: C.I. Pigment Orange 43(C.I. Vat Orange 7); C.I. Pigment Red 194 (C.I. Vat Red 15); perylenepigments: C.I. Pigment Black 31 and 32; C.I. Pigment Red 123, 149, 178,179 (C.I. Vat Red 23), 190 (C.I. Vat Red 29) and 224; C.I. PigmentViolet 29; phthalocyanine pigments: C.I. Pigment Blue 15, 15:1, 15:2,15:3, 15:4, 15:6 and 16; C.I. Pigment Green 7 and 36; pyranthronepigments: C.I. Pigment Orange 51; C.I. Pigment Red 216 (C.I. Vat Orange4); thioindigo pigments: C.I. Pigment Red 88 and 181 (C.I. Vat Red 1);C.I. Pigment Violet 38 (C.I. Vat Violet 3); triarylcarbonium pigments:C.I. Pigment Blue 1, 61 and 62; C.I. Pigment Green 1; C.I. Pigment Red81, 81:1 and 169; C.I. Pigment

vat dyes (in addition to those already mentioned above):

-   -   C.I. Vat Yellow 2, 3, 4, 5, 9, 10, 12, 22, 26, 33, 37, 46, 48,        49 and 50;    -   C.I. Vat Orange 1, 2, 5, 9, 11, 13, 15, 19, 26, 29, 30 and 31;    -   C.I. Vat Red 2, 10, 12, 13, 14, 16, 19, 21, 31, 32, 37, 41, 51,        52 and 61;    -   C.I. Vat Violet 2, 9, 13, 14, 15, 17 and 21;    -   C.I. Vat Blue 1 (C.I. Pigment Blue 66), 3, 5, 10, 12, 13, 14,        16, 17, 18, 19, 20, 22, 25, 26, 29, 30, 31, 35, 41, 42, 43, 35        64, 65, 66, 72 and 74;    -   C.I. Vat Green 1, 2, 3, 5, 7, 8, 9, 13, 14, 17, 26, 29, 30, 31,        32, 33, 40, 42, 43, 44 and 49;    -   C.I. Vat Brown 1, 3, 4, 5, 6, 9, 11, 17, 25, 32, 33, 35, 38, 39,        41, 42, 44, 45, 49, 50, 55, 57, 68, 72, 73, 80, 81, 82, 40 83        and 84;

C.I. Vat Black 1, 2, 7, 8, 9, 13, 14, 16, 19, 20, 22, 25, 27, 28, 29,30, 31, 32, 34, 36, 56, 57, 58, 63, 64 and 65; inorganic pigments: whitepigments: titanium dioxide (C.I. Pigment White 6), zinc white, pigmentgrade zinc oxide; zinc sulfide, lithopone; lead white; black pigments:iron oxide black (C.I. Pigment Black 11), iron manganese black, spinelblack (C.I. Pigment Black 27); carbon black (C.I. Pigment Black 7);chromatic pigments: chromium oxide, chromium oxide hydrate green; chromegreen (C.I. Pigment Green 48); cobalt green (C.I. Pigment Green 50);ultramarine green; cobalt blue (C.I. Pigment Blue 28 and 36);ultramarine blue; iron blue (C.I. Pigment Blue 27); manganese blue;ultramarine violet; cobalt violet and manganese violet; iron oxide red(C.I. Pigment Red 101); cadmium sulfoselenide (C.I. Pigment Red 108);molybdate red (C.I. Pigment Red 104); ultramarine red; iron oxide brown,mixed brown, spinel and corundum phases (C.I. Pigment Brown 24, 29 and31), chrome orange; iron oxide yellow (C.I. Pigment Yellow 42); nickeltitanium yellow (C.I. Pigment Yellow 53; C.I. Pigment Yellow 157 and164); chrome titanium yellow; cadmium sulfide and cadmium zinc sulfide(C.I. Pigment Yellow 37 and 35); chrome yellow (C.I. Pigment Yellow 34),zinc yellow, alkaline earth metal chromates; Naples yellow; bismuthvanadate (C.I. Pigment Yellow 184); interference pigments: metalliceffect pigments based on coated metal platelets; pearl luster pigmentsbased on mica platelets coated with metal oxide; liquid crystalpigments.

Preferred pigments in this context are: perylene pigments,phthalocyanine pigments, indanthrone pigments, isoindoline pigments,quinacridone pigments, interference pigments. Of these, perylenepigments, isoindoline pigments and indanthrone pigments are particularlypreferred.

Examples of particularly preferred pigments are specifically: PigmentBlue 15:1 and 60, Pigment Red 179, Pigment Yellow 139 and Pigment Green7.

Further suitable pigments are mentioned in W. Herbst et al., Industrialorganic Pigments, VCH Weinheim, 1993.

The present invention further provides pigment preparations whichinclude at least one of the compounds of the general formulae I to IIIand at least one inorganic or organic pigment. Preferably the pigmentpreparations further include water. However, water is not a mandatoryingredient.

The pigment preparations may include organic solvents in lieu of or inaddition to water. Useful organic solvents include for example glycolsand glycol ethers such as n-butylglycol and ethylene glycol and alsohigher ethylene glycols HO—(—CH₂—CH₂—)_(n)—OH where is an integer from 2to 50.

The pigment preparations according to the present invention may furtherinclude customary polymeric binders.

In a particularly preferred embodiment, the pigment preparations of thepresent invention include

a) from 0.001 to 97%, preferably from 0.1 to 20% and more preferablyfrom 1 to 15% by weight of at least one of the compounds I, II and/orIII according to the present invention, the aforementioned amounts beingbased on the sum total of the compounds I, II and III,

b) from 1 to 97%, preferably from 2 to 50% and more preferably from 5 to30% by weight of at least one pigment,

c) from 1 to 80%, preferably from 10 to 50% and more preferably from 12to 45% by weight of at least one polymeric binder, and

d) from 1 to 97%, preferably from 5 to 90% and more preferably from 15to 82% by weight of water.

For any one pigment preparation, the percentage fractions add up to 100%by weight.

When the pigment preparations include organic solvents, the organicsolvents fraction is generally in the range from 1 to 97%, preferably inthe range from 1 to 30% and more preferably in the range from 1 to 10%by weight.

All the aforementioned amounts are based on the pigment preparations.

The preparations may include further customary paints and coatingsadditives, for example preservatives, antioxidants, degassers,defoamers, viscosity regulators, thickeners, flow control agents,wetters or surfactants, anti-setters, gloss improvers, glidants,adhesion improvers, skin formation inhibitors, delusterants,emulsifiers, stabilizers, hydrophobicizers, light control additives,hand improvers, antistats, acids, bases and buffers for regulating thepH, dispersants other than the compounds according to the presentinvention and further assistants and auxiliaries familiar to thoseskilled in the art.

According to the present invention, the pigment preparations can be usedin water-containing coatings, printing inks and paints. Water is oneingredient of these coatings, printing inks and paints, but notnecessarily the main constituent of the liquid phase.

In waterborne coatings, by contrast, water is a main constituent andgenerally comprises at least 50% and preferably at least 70% by weightof the coating. According to the present invention, the aforementionedpigment preparations are particularly useful in waterborne coatings. Tothis end, the pigment preparations are formulated for example aswaterborne coating pastes, which customarily include at least 20% andpreferably at least 30% by weight of water.

The aforementioned water-containing coatings, water-containing printinginks and paints and also the waterborne coatings likewise form part ofthe subject matter of the present invention.

The compounds I, II and III according to the present invention, whenused as pigment dispersants, improve the color properties, especiallycolor strength, chroma and transparency. They similarly improve theTheological properties such as yield point and viscosity of the pigmentpreparations. They improve in particular the dispersibility (dispersionharshness) of the pigments. The compounds I, II and III according to thepresent invention can also be used to produce pigment preparations whichdevelop their final color values simply on stirring in a dissolver,without assistance of a stirred media mill.

Even relatively high concentrations of the compounds I, II and III inthe pigment preparations generally do not cause the preparations tobecome gooey or doughy. They reduce the undesirable recrystallization ofpigments and prevent disadvantageous particle growth. They also make itpossible to produce high-pigment pigment preparations.

The compounds I, II and III further facilitate the manufacture ofpigments and thus are very useful as process chemicals in the pigmentmanufacturing operation. A pigment manufacturing operation comprises inparticular:

-   -   a pigment synthesis, including crystallization and subsequent        drying;    -   a wet treatment and subsequent drying step. Here, wet treatment        comprehends for example wet ball milling, kneading with and        without salt or simply stirring of an aqueous suspension, and        drying step comprehends the use of for example a drying cabinet,        a belt dryer, a paddle dryer, a freeze dryer, a spray dryer, a        shaft dryer, a tumble dryer, a fluidized bed dryer, a pneumatic        conveying dryer or a spin flash dryer;    -   dry milling with steel balls.

A number of individual compounds conforming to the formulae I, II andIII also improve the condensation resistance of automotive paintworkowing to their lower solubility and reduced tendency to migrate,compared with prior art dispersants. Finally, some of the compounds Iand II reduce the undesirable blistering during the baking of paintfilms.

The examples which follow illustrate the invention.

EXAMPLES 1. Preparation of Alkyl-capped Oligoalkylene Oxides

a) Oligoalkylene oxides MeOCH₂—CH₂—O)_(a)—OH

The following Pluriol® products from BASF were used. The number ofethylene oxide units (index a) conforms to a distribution. In each case,the main constituent of the product is reported. Me is methyl.

Pluriol A20000E: MeOCH₂—CH₂—O)₄₅—OH

Pluriol A1000E: MeOCH₂—CH₂—O)₂₅—OH

Pluriol A500E: MeOCH₂—CH₂—O)₁₁—OH

Pluriol A350E: MeOCH₂—CH₂—O)₈—OH

Pluriol A275E: MeOCH₂—CH₂—O)₆—OH

b) Oligoalkylene Oxides MeOCH₂—CH₂—O)_(a)—NH₂

b1) Preparation of MeOCH₂—CH₂—O)₁₁—NH₂

A 2.5 l autoclave equipped with a mechanical stirrer was charged with800 g of Pluriol A500E and 200 ml of a ZrO₂/CuO/CoO/NiO catalyst. Thecatalyst had previously been prepared as described in EP-B 382 049 atpage 6 lines 1-16 (“catalyst A”). 400 ml of ammonia were injected at 23°C.; thereafter, hydrogen was injected to a pressure of 50 bar. Afterheating to 175° C., more hydrogen was injected, to a pressure of 200bar. After 24 hours at 175° C. and 200 bar the autoclave was cooled downand depressurized and the contents were filtered to remove the catalyst.Excess ammonia and the water of reaction were removed in a rotaryevaporator. The degree of conversion was determined with reference tothe amine number, which was determined by titration in glacial aceticacid against 0.1 N perchloric acid. The amine number was found to be 597eq.

b2) Preparation of MeOCH₂—CH₂—O)₆—NH₂

The procedure of b1) was repeated using 400 g of Pluriol A275E. Theamine number, determined as in the case of b1), was found to be 296 eq.

2. Preparation of Compounds I, II and III

All the reactions were carried out with absolute tetrahydrofuran (THF)and under dried nitrogen gas, and with stirring. The isocyanate contentwas determined by reacting a sample of the reaction mixture with a 2% byweight solution of dibutylamine in xylene before a potentiometrictitration against 0.1 N hydrochloric acid.

a) Compounds I

Example H1

polymeric compound I where R¹=MeOCH₂—CH₂—O)₄₅ (R⁶=Me),R²=1,5-naphthylene, R³=ethylene, X=O, Y=NH

6.3 g of naphthylene 1,5-diisocyanate (NDI) were dissolved in 200 ml ofTHF by heating. A solution of 0.9 g of ethylenediamine in 50 ml of THFwas added dropwise at 23° C. over 30 min. The white suspension obtainedwas refluxed for 1 hour. Thereafter, a solution of 60 g of PluriolA2000E in 100 ml of THF was added over 30 min. This was followed by afurther hour of refluxing. To destroy any trace isocyanate present, afew drops of ammonia solution were added. The THF was distilled offunder reduced pressure. This provided 681 g of a polymer having amelting point of 270° C.

Example H2

polymeric compound I where R¹=MeOCH₂—CH₂—O)₂₅ (R⁶=Me),R²=tetramethyl-m-xylolene, R³=neopentylene, X=O, Y=O

524.78 g of neopentylglycol and 1 475.22 g of tetramethyl-m-xylenediisocyanate (TMXDI) were dissolved in 2000 g of THF at 25° C., admixedwith 0.52 g of dibutyltin dilaurate and then maintained at 60° C. untilthe isocyanate content had decreased to 2.1%. Thereafter, a solution of2146 g of Pluriol A1000E in 2146 g of THF was added over 1 min. Afteraddition of a further 2.2 g of dibutyltin dilaurate, the reactionmixture was maintained at 60° C. until the isocyanate content haddecreased to 0%. 5200 g of water were added and the THF was distilledoff under reduced pressure. The product obtained was filtered to removewater. This left 4250 g of a viscous polymeric oil.

Example H3

polymeric compound I where R¹=MeOCH₂—CH₂—O)₁₁ (R⁶=Me),R²=1,5-naphthylene, R³=ethylene, X=NH, Y=NH

31.5 g of naphthylene 1,5-diisocyanate were dissolved in 350 ml of THFby heating. A solution of 6 g of ethylenediamine in 50 ml of THF wasadded at 23° C. with cooling over 30 min. The white suspension obtainedwas maintained at 23° C. for 30 min. Thereafter, a solution of 50 g ofMeO+CH₂—CH₂—O)₁,—NH₂ (see above under 1.b1)) in 100 ml of THF was addedover 30 min. The reaction mixture was maintained at 23° C. for a further30 min. To destroy any trace isocyanate, a few drops of ammonia solutionwere added. The THF was distilled off under reduced pressure. Thisprovided 89 g of a polymer having a melting point of 255° C.

Example H4

surfactant compound I where R¹ 32 MeOCH₂—CH₂—O)₈ (R⁶=Me),R²=1,5-naphthylene, no R³ and r=0, X=O, Y missing since r=0

10.5 g of naphthylene 1,5-diisocyanate were dissolved in 200 ml of THFby heating. A solution of 35 g of Pluriol A350E in 100 ml of THF wasadded at 23° C. over 30 min. Any trace isocyanate was destroyed with afew drops of ammonia solution. The THF was distilled off under reducedpressure to leave 46 g of a pasty surfactant.

Example H5

surfactant compound I where R¹=MeOCH₂—CH₂—O)₆ (R⁶=Me),R²=1,5-naphthylene, no R³ and r=0, X=NH, Y missing since r=0

20 g of naphthylene 1,5-diisocyanate were dissolved in 100 ml of THF byheating. A solution of 67 g of MeOCH₂—CH₂—O)₆—NH₂ (see above under1.b2) in 200 ml of THF was added at 23° C. over 30 min. The whitesuspension obtained was diluted with 500 ml of THF and maintained at 23°C. for a further hour. Any trace isocyanate was destroyed with a fewdrops of ammonia solution. The THF was distilled off under reducedpressure to leave 88 g of a pasty surfactant.

b) Compounds II and III

Example H6

polymeric compound III where R¹=MeOCH₂—CH₂—O)₂₅ (R⁶=Me),R²=1,5-naphthylene, R³=ethylene, R⁵=tert-butyl, X=O, Y=NH, Z=NH

47.3 g of naphthylene 1,5-diisocyanate in 500 ml of THF were brieflyheated to the boil under reflux to obtain a homogeneous solution. Asolution of 25 g of Pluriol A1000E in 50 ml of THF was added at 23° C.over 30 min. The clear solution obtained was held at 23° C. for afurther 30 min. Thereafter, a solution of 12 g of ethylenediamine and 50ml of THF was added at 0° C. over 30 min. The white suspension obtainedwas maintained at 23° C. for a further 2 hours. Thereafter, a solutionof 1.9 g of tert-butylamine in 50 ml of THF was added at 23° C. over 1min before the batch was subsequently maintained at 23° C. for a further30 min. Any trace isocyanate was destroyed with a few drops of ammoniasolution. The THF was distilled off under reduced pressure to leave 87 gof a polymer having a melting point of 266° C.

Example H7

surfactant compound II where R¹=MeOCH₂—CH₂—O)₁₂ (R⁶=Me), no R², no R³and r=0, R⁴=naphthyl, X=O, Y missing since r=0

14.8 g of Pluriol A500E were dissolved in 100 ml of THF. A solution of5.0 g of 1-naphthyl isocyanate (monoisocyanate) in 50 ml of THF wasadded at 23° C. over 30 min. The clear solution was subsequentlymaintained at 65° C. for 2 hours. Any trace isocyanate was destroyedwith a few drops of ammonia solution. The THF was distilled off underreduced pressure to leave 27.1 g of a slightly brownish, viscid, clearsurfactant.

Example H8

surfactant compound II where R¹=MeOCH₂—CH₂—O)₆ (R⁶=Me), no R², no R³and r=0, R⁴=naphthyl, X=NH, Y missing since r=0

15.1 g of MeO—(—CH₂—CH₂—O—)₆—NH₂ (see above under 1.b2)) were dissolvedin 100 ml of THF. A solution of 7.0 g of 1-naphthyl isocyanate(monoisocyanate) in 50 ml of THF was added at 23° C. over 30 min. Theclear solution was subsequently maintained at 65° C. for 2 hours. Anytrace isocyanate was destroyed with a few drops of ammonia solution. TheTHF was distilled off under reduced pressure to leave 21 g of a yellowpasty surfactant.

3. Use of compounds I, II and III

The average primary particle sizes were determined from transmissionelectron micrographs.

a) General prescription for preparing the aqueous coating system in awaterborne coating test system

Coating pastes were produced by using the pigment and one of thecompounds H1 to H8 to produce pigment preparations (see examples A1 toA8 hereinbelow). 15 g of each of these pigment preparations weredispersed in 85 g of an aqueous coating system (aqueous anionicallystabilized polyurethane dispersion) on a Skandex shaker from Lau for 2hours. The coating system (polyurethane dispersion) consisted of 23.5 gof polyurethane polymer, 60 g of water and 1.5 g of a 10% by weightsolution of N,N-dimethylaminoethanol in water. The dispersing waseffected in a 250 ml glass bottle using 231 g of SAZ balls 1 mm indiameter.

The waterborne coating paste was white reduced in a ratio of 1:5 with aTiO₂ dispersion (“white testing binder”, consisting essentially of 40%by weight of TiO₂, 20% by weight of anionically stabilized polyurethanedispersion and 40% by weight of water) to produce white reductions. Onthe basis of these white reductions the dispersibility (dispersionharshness) was visually examined under daylight (CIE D65) from aninspection lamp conforming to ASTM D1729 after a dispersing time of 12minutes and after a dispersing time of 120 minutes.

The visual assessments were made in accordance with the table below.TABLE visual assessment of colorations Difference in hue angle dH*,chroma dC*, Coloring Rating lightness dL* equivalents was assessed as 1    0-0.15    98-102 “equal” (basis) 2 >0.15-0.25 “trace” 3 >0.25-0.5 ±3-4 “little” 4 >0.5-1.0 ±5-9 “somewhat” 5 >1.0-2.0 “markedly”6 >2.0-4.0 ±10-20 “distinctly” 7 >4.0 >25 “significantly”

b) Use examples

Example A1

10 g of the compound of example H1 and 50 g of Pigment Blue 60 wereground in the presence of 1.5 kg of grinding balls in a 0.6 litervibrating mill from Siebentechnik for 20 hours. For comparison, 50 g ofPigment Blue 60 were ground under identical conditions without thedispersant. 15 g each of the pigment preparation according to thepresent invention and of the comparative sample were dispersed in theaqueous coating system as described under a) in the generalprescription, and the properties were determined. The pigmentpreparation according to the present invention exhibited betterdispersibility, a distinctly higher color strength after a dispersingtime of 12 min, a markedly redder hue and a markedly cleaner huecompared with the comparative sample.

A dodecaethoxylated β-naphthol as described in EP-A 555 950 did notpermit such a dry ball milling operation, since the compound of EP-A 555950 is liquid.

Example A2

25 g of the compound of example H4 were kneaded with 200 g of PigmentRed 179 which had been finished, ie optimized in its properties bycrystallization, and had an average primary particle size of 50 nm and250 ml of water in an Ilkavisc MKD0,6 laboratory kneader for 36 hours.The kneading viscosity required was adjusted by evaporating or addingwater. The water was subsequently evaporated. For comparison, 200 g ofPigment Red 179 were ground under identical conditions without thedispersant. 15 g of the pigment preparation according to the presentinvention and 15 g of the comparative sample were each dispersed in theaqueous coating system as described under a) in the generalprescription, and the properties were determined. The pigmentpreparation according to the present invention displayed a markedlyhigher color strength and a somewhat cleaner hue than the comparativesample without dispersant.

Example A3

13.5 g of Pigment Blue 15:1 (average primary particle size 25 nm) weremanually preblended with 1.5 g of the compound of example H7. Thispigment preparation was dispersed in the above aqueous coating system asper the above general prescription, and the properties were determined.The coating according to the present invention exhibited a somewhathigher color strength and markedly higher chroma than a comparativecoating which contained 15 g of the pigment and no compound according tothe present invention.

Example A4

100 g of Pigment Red 179 (average primary particle size 2 μm) wereground with 20 g of the compound of example H3 in the presence of 1.5 kgof steel grinding balls 3 cm in diameter in a planetary mill for 36hours. For comparison, 120 g of Pigment Red 179 were ground underidentical conditions without the dispersant. 15 g each of the pigmentpreparation according to the present invention and of the comparativesample were dispersed in the aqueous coating system as described undera) in the general prescription, and the properties were determined. Thepigment preparation according to the present invention exhibited betterdispersibility, a substantially higher color strength, a markedlycleaner hue and a somewhat yellower hue compared with the comparativesample without dispersant.

A dodecaethoxylated β-naphthol as described in EP-A 555 950 did notpermit such a dry ball milling operation, since the compound of EP-A 555950 is liquid.

Example A5

20 g of Pigment Yellow 139 (average particle size 150 nm) were wetground with 4 g of the compound of example H5 in 100 ml of water in thepresence of 20 g of 3 mm glass balls in a Skandex shaker from Lau for 4hours. After the glass balls had been filtered off, the suspensionobtained was evaporated to dryness in a drying cabinet at 80° C. Agranular product was obtained. 15 g of this granular product wereredispersed in the aqueous coating system as described, and theproperties were determined. The coating according to the presentinvention had a somewhat higher color strength, a somewhat greener hueand somewhat higher chroma after a dispersing time of 12 min and after adispersing time of 120 min than a comparative composition withoutdispersant.

Example A6

10 g of the compound of example H6 and 50 g of Pigment Green 7 wereground in the presence of 1.5 kg of 1 mm steel balls in a vibrating millfor 36 hours. For comparison, 60 g of Pigment Green 7 were ground underidentical conditions without addition of dispersant. The two sampleswere dispersed in the aqueous coating system as per the abovementionedgeneral prescription, and the properties were determined. The samplecontaining H6 had a distinctly higher color strength, a lowerdispersibility (significantly higher color strength after a dispersingtime of 12 minutes) and a little higher chroma than the comparativesample.

A dodecaethoxylated β-naphthol as described in EP-A 555 950 did notpermit such a dry ball milling operation, since the compound of EP-A 555950 is liquid.

Example A7

20 g of Pigment Blue 60 in the form of a moist presscake were dispersedwith 2 g of the compound of example H8 in a total of 100 ml of water inthe presence of 20 g of 3 mm glass balls in a Skandex shaker from Laufor four hours. For comparison, a dodecaethoxylated β-naphthol,described in EP-A 555 950, was used in lieu of the compound of exampleH8. After the glass balls had been removed, the fluidic pigmentsuspension was dried at 80° C. The two samples were dispersed in theaqueous coating system in accordance with the above general description,and the properties were determined. The sample containing H8 had asomewhat higher color strength and a somewhat higher chroma.

Example A8

20 g of the compound of example H2 were kneaded with 200 g of PigmentRed 179 which had been finished, ie optimized in its properties bycrystallization, and had an average primary particle size of 150 nm and250 ml of water in an Ilkavisc MKD0,6 laboratory kneader for 10 hours at15° C. and 12 Nm torque. The kneading viscosity required was adjusted byevaporating or adding water. The water was subsequently evaporated. Forcomparison, 200 g of Pigment Red 179 were ground under identicalconditions without the dispersant. 15 g of the pigment preparationaccording to the present invention and 15 g of the comparative samplewere each dispersed in an aqueous coating system as described under a)in the general prescription, and the properties were determined. Thepigment preparation according to the present invention displayed amarkedly higher color strength and a somewhat cleaner hue than thecomparative sample without dispersant.

1. Compounds of the general formulae I to IIIR¹—X—[—CO—NH—R²—NH—CO—Y—R³—Y—]_(r)—CO—NH—R²—NH—CO—X—R¹  (I)R¹—X—[—CO—NH—R²—NH—CO—Y—R³—Y—]_(r)—CO—NH—R⁴  (II)R¹—X—[—CO—NH—R²—NH—CO—Y—R³—Y—]_(r)—CO—NH—R²—NH—CO—Z—R⁵  (III) were R¹ isan alkyl-capped oligoalkylene oxide radical of the general formula IVR⁶O—(—CH₂—CH₂—O—)_(a)—(—R⁷—O—)_(b)—  (IV) where X is O or NH Y is O orNH Z is O or NH R² is an arylene or aralkylene radical of an aliphatic,aromatic or aromatic-aliphatic diisocyanate OCN—R²—NCO, R³ is analkylene, arylene or aralkylene radical of an aliphatic, aromatic oraromatic-aliphatic diol HO—R³—OH for Y being O or a diamine H₂N—R³—NH₂for Y being NH, R⁴ is an alkyl, aryl or aralkyl radical of an aliphatic,aromatic or aromatic-aliphatic monoisocyanate R⁴—NCO, R⁵ is an alkyl,aryl or aralkyl radical of an aliphatic, aromatic or aromatic-aliphaticmonoalcohol R⁵—OH for Z being O or a monoamine R⁵—NH₂ for Z being NH, R⁶is alkyl of 1 to 4 carbon atoms, R⁷ is branched alkylene of 3 to 8carbon atoms, r is a rational number from zero to 100, a is an integerfrom 1 to 300, and b is an integer from zero to
 30. 2. Compounds asclaimed in claim 1, wherein R⁶ is methyl.
 3. Compounds as claimed inclaim 1, wherein r is zero.
 4. Compounds as claimed in claim 1, whereinR² is selected from the group consisting of —(—CH₂—)₆—,


5. Compounds as claimed in claim 1, wherein R³ is selected from thegroup consisting of


6. Compounds as claimed in claim 1, wherein a is an integer from 1 to300 and b is zero.
 7. A process for preparing a compound of the formulaI claimed in claim 1, which comprises reacting a diisocyanate OCN—R²—NCOwith a diol HO—R³—OH, when Y is O or with a diamine H₂N—R³—NH₂, when Yis NH and with an alkyl-capped oligoalkylene oxide of the generalformula IVa when X is O,R⁶O—(—CH₂—CH₂—O—)_(a)—(—R⁷—O—)_(b)—OH  (IVa) or the general formula IVbwhen X is NH,R⁶O—(—CH₂—CH₂—O—)_(a)—(—R⁷—O—)_(b)—NH₂  (IVb).
 8. A process forpreparing a compound of the formula II as claimed in claim 1, whichcomprises reacting a diisocyanate OCN—R²—NCO with a diol HO—R³—OH, whenY is O or with a diamine H₂N—R³—NH₂, when Y is NH and with analkyl-capped oligoalkylene oxide of the general formula IV when X is O,R⁶O—(—CH₂—CH₂—O—)_(a)—(—R⁷—O—)_(b)—OH  (IVa) of the general formula IVbwhen X is NH,R⁶O—(—CH₂—CH₂—O—)_(a)—(—R⁷—O—)_(b)—NH₂  (IVb) and also with amonoisocyanate R⁴—NCO.
 9. A process for preparing a compound of theformula III as claimed in claim 1, which comprises reacting adiisocyanate OCN—R²—NCO with a diol HO—R³—OH, when Y is O or with adiamine H₂N—R³—NH₂, when Y is NH and with an alkyl-capped oligoalkyleneoxide of the general formula IV when X is O,R⁶O—(—CH₂—CH₂—O—)_(a)—(—R⁷—O—)_(b)—OH  (IVa) or of the general formulaIVb when X is NH,R⁶O—(—CH₂—CH₂—O—)_(a)—(—R⁷—O—)_(b)—NH₂  (IVb) and also, when Z is O,with a monoalcohol R⁵—OH or, when Z is NH, with a monoamine R⁵—NH₂. 10.A method of using, which comprises: combining at least one compound ofclaim 1 with at least one pigment.
 11. (Cancelled).
 12. Pigmentpreparations comprising: at least one compound as claimed in claim 1, atleast one inorganic or organic pigment and optionally water. 13-14.(Cancelled).
 15. Water-containing coatings, water-containing printinginks, water-containing paints and waterborne coatings including pigmentpreparations as claimed in claim
 12. 16. A water-containing coating,ink, or paint, comprising: at least one compound as claimed in claim 1at least one inorganic or organic pigment and optionally water.
 17. Awaterborne coating, comprising: at least one compound as claimed inclaim 1 at least one inorganic or organic pigment and optionally water.